Craze resistant resinous coating, coated product, and process of making it



Patented Sept. 2, 1952 CRAZE RESISTANT RESINOUS COATING,-

COATED PRODUCT, AND PROCESS. O-

MAKING IT Donald G. Patterson, Darien, Conn., assignor to S American Cyanamid Company, N. Y., a corporation of Maine New York,

No Drawing. Application May 7, 1948,

Serial No. 25,806 r 10 Claims. (Cl. 154-121) resinous coating, a coated product, and the process of making it.

This application is a continuation-in-part of Serial No. 575,572, filed January 31, 1945, now abandoned.

Laminated materials have previously been made by first producing a core or base, preferably aper laminated with a synthetic resin, usually phenol-formaldehyde resin, and thereafter applying a surface coating of thermosetting aminoplastic resin selected from the group consisting of urea-formaldehyde resins and melamine-formaldehyde resins. Frequently, this coated sheet is superimposed upon a plurality of phenolic impregnated plies, and the whole assembly cured and bonded in one single operation. Often one or more sheets of paper impregnated with one or more of the thermosetting aminoplastic resins is included in the surface coating. Many of these laminated materials have been found to craze, and many attem tshave been made to prevent this by the use of modifiers, such as plasticizers, for the urea-formaldehyde and melamine-formaldehyde resins. The-use of paper fibers has been proposed by Cochrane, U. S. Patent No. 2,038,345, and Guhl, U. S. Patent No. 2,292,118. None of the products heretofore employed have been free from crazing, particularly when such products have been subjected to varying atmospheric conditions, particularly variations in temperature and humidity conditions, over a relatively long period of time. In other words, many products have been prepared which do not craze initially, but which do craze after a relatively short period of use.

An object of the present invention, therefore, is toprovide laminated materials having a coating thereon, which will not craze under variations of atmospheric conditions, such as temperature and humidity. Another object of the present invention is to provide a process for preparing laminated materials to produce a craze resistant surface on a surface thereof. A still further object of the present invention is to provide a craze resistant resinous coating. Included within the scope of the present invention, is the object to produce laminated materials havin surfaces which do not exhibit cracking or crazing, even after exposure to varying atmospheric conditions.

The foregoing and other objects of this invention are obtained by incorporating glass fibers into a thermosetting aminoplastic coating composition selected from-the group consisting of melamine-formaldehyde and urea-formaldehyde 2 resins dispersed in a volatile vehicle. which may or may not havepigmentincorporated therein; and, applying this composition to a fibrous sheet and curing the composition on a'core which may be preformed laminated'materiahor a plurality of laminae in assembled condition, ready for bonding. The coating composition may also be applied to a preformed fibrous laminated material in the absence of an additional coating surface sheet. It is more convenient, however, to employ a carrier sheet in preparing a surfaced core.

The following examples in which the proportions are in parts by weight, are given wholly by way as illustration, and not in limitation.

Example 1 Twenty-four (24) parts of a melamine-formaldehyde resin (Resin A), 8 parts of glass fiber, 8 parts of titanium dioxide. 36 parts of ethanol, and 24 parts of water were blended together and ground ina pebble mill for about 6-18 hours to produce a homogeneous coating composition.

A composition prepared in accordance with the foregoing description is sprayed on to the surface of a paper laminate which is bonded together with a phenol-formaldehyde resin. The coated laminate is placed in an oven to dry for about 10 minutes at C. and for 45 minutes at C. The laminate surface is then cured by pressing at 1100 p. s. i. and at C. for about 20 minutes. A smooth, craze resistant, glossy white surfaced laminate is obtained. Even after several cycles of alternate exposure of the laminate to steam for one-half hour, and to atomperature of 105 C. in an oven for one-half hour, the laminate shows no crazing visible to the naked eye.

Example. 2

. Five (5) parts of melamine-formaldehyde resin (Resin A), 3 parts of glass fiber, 2 parts of titanium dioxide, 15 parts of butanol and 6 parts of water are blended together, ball milled to efiect a smooth dispersion, and applied to a laminate and dried prior to curing, the resin employed for bonding the laminate. After curing, both the surface and bonding resins in accordance with the procedure of Example 1, the laminate has a glossy, hard, craze resistant coating. It will withstand 10-15 cyclesof the test described in Example 1 without crazing visible to the naked eye. No crazing is found after '7 days in a sweat box at 105 F. and 100% relative humidity, nor

after 4 weeks in an oven at 105 C.

Example .3

A composition of 80 parts. melamine-formaldehyde resin (1:2 mol ratio), 80 parts fine glass fibres, 40 parts titanium dioxide pigment, 385 parts water, and parts n-butanol were dispersed by ball milling for 16 hours. This smooth paste obtained in this manner was coated on a pigmented alpha cellulose paper which had previously been impregnated with'a melamine -formaldehyde resin solution and dried. The 'coa'ted paper was dried for 8 minutes at 103 C. to remove the solvent. The coat spread ofthis co rnposition was 20 grams per 'sdua re 'f oot'of paper surface. The coated paper was then superimposed upon a plurality of phenolic resin impregnated Kraft paper plies and the a'ssembly'united under heat and pressure of 150 C. and 1100 ps. i.

The laminate obtained in this for 10 minutes. manner was satisfactorily united and bonded and had asurface of excellent smoothglosahaving no-cracks amazes, aha, afterfbeiiigsiibjcted t the tst of ait'r'iiatiiigj dsure in steam 'at atmospheric press ui e'and 'd heat"at 105'C.,. 15 minutes ineach condition indibitd for 10 cycles, there was no name Brennan cracking after 10 cycles. I 7

Where hard p niiits are used, the'pigment may be g roii ndin"thefresinpridr tog'rinding in the g'las's'fio'ck. I

,Thfe surraceddla'ti'rig may: be applied either be fore or aftert'h'e amazes bonded together by curing the resin with which the plies of the lamina'teare impregnated.

Eighteen hundred fifty (1850) parts of formalin (37 forz naldeh yde) and 1390 parts of melamin ar hew d. n o. a. i i tabl tem g vessel provided with an agitator and arefiux condenser. The pI-l pfthe mixture is adiiisted to fl'with soe h iio ii' eand .th nfls ze is "i n he to efl x e p fmat l fififil- Thi t m utes afterreacliing 'refflux, the mixture is cooled to 75 C. and the-p11 is "adjusted to -10"with sodium hydroxide. Ab oiit ll) parts of a filter-aid are added and the mixture is :filtered'after which the filtrate placed in an ev'aporatorandthe s r i s e eb fihl i ches of er r s u e. es r'e- Th rn e n t a o a o s t h a d to "be i a. a i fl hei t s em ature or the syrupfraches about107 C5103 C. it is'dischargedintotrays andcooled lat about 13 C. untilahardres'in isobtained. The resin isg-roun,dtoforn1afineipowder H v 4 H ln'place a: the melamine-formaldehyde resin used in the prfeceding examples, replay employ other melamine-formaldehyde condensation products containing 1 or more mols of formaldehyde per mol of melamine. In order to obtain products which have especially high chemical resistance "and good physical properties, it is preferable that the formaldehydemelaniine ratio be between about 1511.0 and :10. Ureaformaldehyde resins may also .be used inaccordance with this invention and those having a formaldehyde-ratio between about 1.3 2 -1 and 2 1 are suitable. Resins suitable for'this invention are those which are soluble in water "or alcohol or in mixtures thereof.

Glass fibers having diameters rangin'g from about 4-11 micronsmaybe used in-the-above example. When s'uch. fibers are fused, theweight ratio of resin to glass is preferably-between-about 1:1 and 9:1, but when fibers ofsmaller diameter are used, the ratio of glass to resin may :be reduced and yet obtain similar results. With fibers having a diameter of less than 1 microns, the weight ratio of glass to resin may be as low as 1:99, although generally, it willbe found desirableto employ weight ratios'of glass toresin near 1:10, and preferably not less than 1 :35. For optimum results, the glass fibers should :be free from lubricant, which exists as a result of the same fiber manufactures. If the lubricant interferes with adhesion of resin to the glass fibers, a good surfaoeisjnot obtained, and, therefore, the

glass should be'cleaned, as for example by stovtrig orby extratibn with carbon tetrachloride or heat-treating. Such cleaning is not necessary, however, when lubricant free fibers are obtained and used.

7 This invention may be practiced with or without pigment. Since, however, most applications of the present invention require pigmented surfaces, and since pigmented surface films are most susceptible to surface cr'a'cking "or erazing, "the amount of pigment employed shouldbei'i'sd with discretion. It is quite true that large pi dportio'ns of pigment in'ay beeinployed int'he compositions of the present invention, but from an-econozi-iical viewpoint, as well as fromapractic'al'vfewpbint, it is desirable thatnot more'than apart of pigment be employed per' part'of'res'in, aiidforbptim'um "results withrespect to "craze "stance, hiding coverage arid-character and o'f surfaca'itis desirableto' einpIQyOA to Spa'r't's of pigment per part 'o'i res'in. when small proportion of glass fibi s aie 'employed fdr example, less than 10%, basd 'dn the-'weight b'f resin, it is prerera blaii nonessential, thnt 'slilall diameter glass fibls "be mpio eu, i. 8;, 131165}? fibers having atiiainetr qessthan' i ii-iif'o'nsfiand that a relatively low ratiooflpigiiintlto rsinbe employed. Satisfactory -i'esults; ai'e obtaihed-Hn these low fiber com ositions, Wile n the piginent approximately fli'a'sed on the wig'l'it of resin, 7 i I I The coating tem os bills dlic d V ance with this invention may ta n 'a w'ide variety of 'dyesQQg'nih-tsjdr'fliers-in a canto the melamine-formaldehyde resins and-"glass fi bers. By'varyiiig "the pi'g irients-End dy'esf-it is possible to obtain'nianydiifrent colored nsterials. While this ention ha's b'en ticularly with refere ce" to the pplicat'ioir-of these coating adapters-611s tofa p fo'ii'n lan'ii- Hate bonded with phi idbfiifinal'dhyde resin, it may also be used as an"iinpregnating xnaterial for paper to form a- -l'a "ate b'onc'id 'sdlely w'ith the composition. Fore t'my' jreassnsyaregenerally desirable, never, tense a base'rnaterial which is Bonus "with a phehoI fQimaIdehyii'e resin, a urea-for cihyde'"rsinfor'with some other relatively inexpensi've-"'esin, butanyresm suitable for' boiidiiig the plies-of a laniinate fiiay he used. i

This invention facture of 'la'rn in ent purposes, dishes, 'traysfief" examples. t t

These boating" cohipsitions-niay beapplied"to pulp preforins-brtblaininatedinaterials, 'tlieresin bond of which is cured or uncured, byspraying, by roll boatin 'or by" any other suitable means. The'y' iiiijbehblle'd steamy to paper laminates but secretly-wood or laniih'atescontaining cloth. I rneseo ting' caimpcsitionsway statesma also be applied to a fibrous carrier sheet,} preferably 'thermosettingresin impregnated paper, and employ this 'coatedsheet to" surface any suitable core, such as" fibrous laminates, pressed jwood, and the like. I if v 7 T The term crazing as used herein is intended to denote the surface cracks visible to the naked eye, but does not include any fine cracks or lines which are not visible to'the naked eye butwhich may be seen under microscopical examination.

Obviously, many modifications and variations in these processes and compositions may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim: 1. A process for producing a laminated product having a craze resistant surface which comprises applying to the surface sheet of a laminate a thermosetting synthetic resin selected from the group consisting of urea-formaldehyde resins and melamine-formaldehyde resins, pigment and glass fibers in a volatile vehicle, drying said surface sheet and applying heat and pressure to said coating surface to produce a body having a substantial insoluble, infusible, craze resistant continuous film on the surface thereof, wherein said volatile vehicle is a solvent for the resin selected from the group consistingof water and an alcohol and is present in a weight ratio of said vehicle to said resin of between 1.5: 1 to :1, and wherein said glass fibers and said resin are present in a weight ratio between 1:1 and 1:9, respectively, and wherein said glass fibers have a diameter of between 4-11 microns.

2. A process for producing a laminated product having a craze resistant surface which comprises applying to a laminate, a surface sheet coated with a melamine-formaldehyde resin and glass fibers in a volatile vehicle, drying said sheet and consolidating the assembly under heat and pressure to produce a body having a substantial insoluble, infusible, craze-resistant, continuous film on its surface, wherein said volatile vehicle is a solvent for the resin selected from the group consisting of water and an alcohol and is present in a weight ratio of said vehicle to said resin of between 1.5 1 to 5: 1, and wherein said glass fibers and resin are present in a weight ratio of between 1:1 and 1:9, respectively, and wherein said glass fibers have a diameter of between 4-11 microns.

3. A process for producing a laminated product having a craze resistant surface which comprises applying to a laminate, a surface sheet coated with a melamine-formaldehyde resin and glass fibers in a volatile vehicle, drying said sheet and consolidating the assembly under heat and pressure to produce a body having a substantial insoluble, infusible, craze-resistant, continuous film on its surface, wherein said volatile vehicle is a solvent for the resin selected from the group consisting of water and an alcohol and is present in a weight ratio of said vehicle to said resin of between 1.5:1 to 5:1, and wherein said glass fibers and resin are present in a weight ratio of between 1:1 and 1:9, respectively, and wherein said glass fibers have a diameter of between 4-11 microns, and wherein said melamine-formaldehyde resin has a mol ratio of 1.5-3.5 mols of formaldehyde per mol of melamine.

4. A process for producing a laminated product having a craze resistant surface, which comprises applying to asurface sheet of a laminate, a melamine-formaldehyde resin and glass fibers dispersed in an aqueous solution of ethanol, drying' said-surfs;

ass-at I I W applyifig heat and pressure to said datedsurface to'produce a'body having" a' substantialiiisoluble, infusible, crazeresistant continuous filin on the surface thereof,

wherein said gassnters and saidresin are present-in a weight ratio between 1;: 1 and 1:9, wherein said glass fibers have a diameter size of between 4-1-1.microns and'wherein" the weight ratio of the resin to the aqueous vsolution of ethanol is 122.5, rspectively.

' 5. A'sheet of'cellulosic fibrous material coated with a melamine-formaldehyde resin and glass fibers dispersed in a volatile vehicle selected from the group consisting of water and an alcohol wherein the weight ratio of said vehicle to said resin is between 1.5:1 and 5:1 and wherein said fibers have a diameter of between 4-11 microns and are present in a weight ratio with said resin of between 1:1 and 1:9, respectively.

6. A sheet of cellulosic fibrous material coated with a melamine-formaldehyde resin and glass fibers dispersed in a volatile vehicle comprising an aqueous solution of ethanol, wherein the weight ratio of said vehicle to said resin is 2.5:1 and wherein said fibers have a diameter of between 4-11 microns and are present in a weight ratio with said resin of between 1:1 and 1:9, respectively.

7. A paper laminate having an exterior surface thereof coated with a composition comprising a melamine-formaldehyde resin and glass fibers wherein said glass fibers have a diameter of between 4-11 microns and wherein said resin and said glass fibers are present in a weight ratio of 1:1 and 9:1, respectively.

8. A resinous composition adapted to form a hard, craze-resistant coating on the surface of laminated articles comprising a uniform mixture of melamine-formaldehyde resin and glass fibers dispersed in a volatile vehicle selected from the group consisting of water and an alcohol, wherein the weight ratio of vehicle to resin is between 1.5:1 to 5:1, wherein said glass fibers have a diameter of between 4-11 microns and wherein the weight ratio of said resin to said fibers is between 1:1 to 9:1, respectively.

9. A resinous composition adapted to form a hard, craze-resistant coating on the surface of laminated articles comprising a uniform mixture of melamine-formaldehyde resin and glass fibers dispersed in a volatile vehicle comprising an aqueous solution of ethanol, wherein the weight ratio of vehicle to resin is 2.5:1, respectively, wherein said glass fibers have a diameter of between 4-11 microns and wherein the weight ratio of said resin to said fibers is between 1:1 and 9:1, respectively.

10. A process for producing a laminated product having a craze resistant surface which comprises applying to the surface sheet of a laminate a thermosetting synthetic resin selected from the group consisting of urea-formaldehyde resins and melamine-formaldehyde resins, and glass fibers in a volatile vehicle, drying said surface sheet and applying heat and pressure to said coating surface to produce a body having a substantial insoluble, infusible, craze resistant continuous film on the surface thereof, wherein said volatile vehicle is a solvent for the resin selected from the group consisting of water and an alcohol and is present in a weight ratio of said vehicle to said resin of between 1.5:1 to 5:1, and wherein said glass fibers and said resin are present in a weight ratio between 1:1 and 1:9, re-

spectively, and wherein :said' glasskfibemhave a. Number V Name Date diameter ofbetweenfijlrmicrons. 2;290;1-3 3;": ,Swain et. a1; July 1:4, 19.42 IDONAI QDZG. PATTERSON. 2292118 I Guhl L Aug. 4, 1942 V i j 2,344,733 Ripper Mar. 21, 1944 REFERENCES CITED f 5 2,377,867 DAlelio June '12, 1945 'The following references are of record in =the 2,385,334 sept- 25, 1945 this at nt; I 2,428,654 Colhns :Oct. 7,1947

:um mnsmms mmms 1 r THER REFERENCES Number Name *Date 10 .MQdern PIaSticS reprint, vol. '21, No. 9"-(May 

1. A PROCESS FOR PRODUCING A LAMINATED PRODUCT HAVING A CRAZE RESISTANT SURFACE WHICH COMPRISES APPLYING TO THE SURFACE SHEET OF A LAMINATE A THERMOSETTING SYNTHETIC RESIN SELECTED FROM THE GROUP CONSISTING OF UREA-FORMALDEHYDE RESINS AND MELAMINE-FORMALDEHYDE RESINS, PIGMENT AND GLASS FIBERS IN A VOLATILE VEHICLE, DRYING SAID SURFACE SHEET AND APPLYING HEAT AND PRESSURE TO SAID COATING SURFACE TO PRODUCE A BODY HAVING A SUBSTANTIAL INSOLUBLE, INFUSIBLE, CRAZE RESISTANT CONTINUOUS FILM ON THE SURFACE THEREOF, WHEREIN SAID VOLATILE VEHICLE IS A SOLVENT FOR THE RESIN SELECTED FROM THE GROUP CONSISTING OF WATER AND AN ALCOHOL AND IS PRESENT IN A WEIGHT RATIO OF SAID VEHICLE TO SAID RESIN OF BETWEEN 1.5:1 TO 5:1, AND WHEREIN SAID GLASS FIBERS AND SAID RESIN ARE PRESENT IN A WEIGHT RATIO BETWEEN 1:1 AND 1:9, RESPECTIVELY, AND WHEREIN SAID GLASS FIBERS HAVE A DIAMETER OF BETWEEN 4-11 MICRONS.
 8. A RESINOUS COMPOSITION ADAPTED TO FORM A HARD, CRAZE-RESISTANT COATING ON THE SURFACE OF LAMINATED ARTICLES COMPRISING A UNIFORM MIXTURE OF MELAMINE-FORMALDEYDE RESIN AND GLASS FIBERS DISPERSED IN A VOLATILE VEHICLE SELECTED FROM THE GROUP CONSISTING OF WATER AND AN ALCOHOL, WHEREIN THE WEIGHT RATIO OF VEHICLE TO RESIN IS BETWEEN 1.5:1 TO 5:1, WHEREIN SAID GLASS FIBERS HAVE A DIAMETER OF BETWEEN 4-11 MICRONS AND WHEREIN THE WEIGHT RATIO OF SAID RESIN TO SAID FIBERS IS BETWEEN 1:1 TO 9:1, RESPECTIVELY. 